EP2588484B1 - Organic compound and electrochromic device including the same - Google Patents

Organic compound and electrochromic device including the same Download PDF

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EP2588484B1
EP2588484B1 EP11800650.1A EP11800650A EP2588484B1 EP 2588484 B1 EP2588484 B1 EP 2588484B1 EP 11800650 A EP11800650 A EP 11800650A EP 2588484 B1 EP2588484 B1 EP 2588484B1
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group
compound
groups
carbon atoms
organic compound
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EP2588484A1 (en
EP2588484A4 (en
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Kenji Yamada
Shinjiro Okada
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Canon Inc
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Canon Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Definitions

  • the present invention relates to a novel organic compound and an electrochromic device including the same.
  • electrochromic hereinafter may be abbreviated as "EC" materials of which optical absorption properties (colored state and light transmittance) are changed by an electrochemical oxidation-reduction reaction.
  • Metal oxides such as WO 3
  • inorganic EC materials are known as inorganic EC materials, but they have a problem in that the method of forming a film thereof is limited to, for example, deposition, which prevents the film from being formed over a large area.
  • Organic EC materials are described in, for example, PTL 1 disclosing an EC device including an electrically conductive polymer and PTL 2 disclosing an EC device including an organic low-molecular-weight compound such as viologen.
  • the electrically conductive polymer described in PTL 1 can be directly formed as an EC layer on an electrode by electropolymerization of a monomer.
  • the electrically conductive polymer that forms the EC layer for example, polythiophene, polyaniline, and polypyrrole are known.
  • electrochemical oxidation or reduction thereof changes the ⁇ -conjugated chain length of the main chain, the electronic state of the highest occupied molecular orbital (HOMO), and the absorption wavelength.
  • HOMO highest occupied molecular orbital
  • These electrically conductive polymers have ⁇ -conjugated systems and show absorptions in the visible light region in neutral states. Therefore, they have colors, and the absorption wavelengths shift to the longer wavelength side (infrared region side) by oxidation. The absorption in the visible light region disappears by the shift to the infrared region side, and thereby the EC device loses its color.
  • organic EC materials are low in stability and may not be sufficiently bleached even in the bleached states.
  • the electrically conductive polymer in the neutral state has an absorption band in visible light. Accordingly, if there is a portion in which the electrochemical reaction is insufficient, remnant occurs to make it difficult to obtain high transparency.
  • viologen EC compound of PTL 2 repetition of deposition and dissolution results in a deterioration phenomenon, which is thought to be caused by insolubilization due to irreversible crystallization or polymerization. This deterioration causes "remnant" in which transparency is not obtained even in the bleached state.
  • the viologen EC compound generates an unstable radical cation when reduced and, thereby, has a problem of being unstable.
  • JP 2006-089413 A discloses the following compounds:
  • JP 2009-215333 A discloses compounds having the following base structure:
  • the present invention provides an organic compound that is stable even in the radical cation state and against repetition of oxidation-reduction and that also has high transparency not having optical absorption in the visible light region in the bleached state. Furthermore, the present invention provides an EC device including the organic compound.
  • a and A' are each independently selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups; and at least one of A and A' is selected from the alkyl groups, the alkoxy groups, and the aryl groups.
  • the aryl groups may each have an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms as a substituent.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an amino group, or a silyl group; and n is 1 or 2.
  • the aryl group, the aralkyl group, the amino group, and the silyl group may each have an alkyl group having 1 to 4 carbon atoms as a substituent.
  • an organic compound having high stability against repetition of an oxidation-reduction reaction and discoloring in the electrically neutral state and thereby having high transparency not to cause remnant in the visible light region.
  • the organic compound according to the present invention is represented by the following General Formula [1]:
  • a and A' are each independently selected from hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups, and alkoxy groups, and at least one of A and A' is selected from the alkyl groups, the aryl groups, and the alkoxy groups.
  • the aryl groups may each have an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms as a substituent.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an amino group, or a silyl group; and n is 1 or 2.
  • the aryl group, the aralkyl group, the amino group, and the silyl group may each have an alkyl group having 1 to 4 carbon atoms as a substituent.
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by A or A' include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a pentyl group, an octyl group, a dodecyl group, a cyclohexyl group, a bicyclooctyl group, and an adamanthyl group.
  • Examples of the alkoxy group represented by A or A' include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, a t-butoxy group, an ethylhexyloxy group, an octyloxy group, and a decyloxy group.
  • the hydrogen atom in the alkyl group may be substituted with a fluorine atom into, for example, a trifluoromethyl group.
  • alkyl groups can have a smaller number of the carbon atoms.
  • the alkyl group can be a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, in particular, can be a methyl group, an ethyl group, or an isopropyl group.
  • Examples of the aryl group represented by A and A' include a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a naphthyl group, a fluoranthenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a perylenyl group.
  • the aryl group can be a phenyl group or a biphenyl group.
  • Examples of the optional substituent of the aryl group include halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups, aryl groups, aralkyl groups, substituted amino groups, and substituted silyl groups.
  • Specific examples of the alkyl group and the aryl group are the same as those of the alkyl group and the aryl group as the above-described substituents represented by A or A'.
  • a hydrogen atom may be substituted with a fluorine atom.
  • At least one of A and A' is selected from the above-mentioned alkyl groups and the aryl groups.
  • the substituent represented by A or A' can be bulky.
  • the substituent can be a phenyl group, a biphenyl group, an isopropyl group, a t-butyl group, or a dodecyl group.
  • the phenyl group and the biphenyl group may have an alkyl group as a substituent.
  • the other may be a hydrogen atom.
  • Examples of the alkyl group and the aryl group as the substituents represented by R 1 and R 2 are the same as those of the alkyl group and the aryl group as the above-described substituents represented by A or A'.
  • Other examples of the substituents represented by R 1 and R 2 include alkoxy groups such as a methoxy group, an ethoxy group, an octyloxy group, and a decyloxy group; aralkyl groups such as a benzyl group and a phenylethyl group; substituted amino groups such as a dimethylamino group and a diphenylamino group; and substituted silyl groups such as a trimethylsilyl group and a triisopropylsilyl group.
  • the substituent represented by R 1 or R 2 can be particularly a methyl group, an ethyl group, a methoxy group, or a dimethylamino group, which have high electron-donating properties.
  • substituents represented by R 1 or R 2 can be introduced at the para-position of the phenyl group that binds to dithienothiophene, in order to inhibit side reactions, such as electropolymerization, accompanied by oxidation-reduction.
  • the organic compound according to the present invention is composed of a dithienothiophene structure of the core serving as an optical absorption portion and a structure in which phenyl groups having substituents at the ortho-positions are introduced at the 2-position and the 6-position of the dithienothiophene.
  • the dithienothiophene structure serving as the core of the structure of the organic compound according to the present invention is the optical absorption portion in the organic compound according to the present invention.
  • This dithienothiophene structure has a structure in which three thiophene rings are condensed.
  • a compound including one or two repeating dithienothiophene units i.e., n represents 1 or 2
  • n represents 1 or 2
  • n represents 1 or 2
  • the organic compound according to the present invention in the neutral state has optical absorption in the ultraviolet region and does not have absorption in the visible light region and thereby shows high transparency.
  • the compound in the oxidized state has optical absorption in the visible light region, being in the colored state.
  • electrically conductive polymers have optical absorption in the visible light region in the neutral state, "remnant", an absorption band in the visible light region, occurs in a portion where the electrochemical reaction is insufficient even in the oxidized state.
  • the compound according to the present invention can maintain high transparency not having an absorption band in the visible light region even if a portion where the electrochemical reaction is insufficient is present.
  • Dithienothiophene has high molecular planarity. This has an effect by the resonance structure of enhancing the stability of the radical cation, which is generated in the oxidized state.
  • phenyl groups having substituents at the ortho-positions are introduced at the 2-position and the 6-position of the dithienothiophene.
  • the compound is characterized by having an effect of protecting the dithienothiophene skeleton that generates a radical cation by steric hindrance of the introduced bulky phenyl groups having substituents at the ortho-positions.
  • the instability of radical cations is caused by, for example, recombination between radicals due to high reactivity of the radicals or hydrogen abstraction from another molecule by the radical. That is, the instability is caused by a reaction of a radical due to a contact of the radical with another molecule.
  • the steric hindrance of the phenyl groups having substituents at the ortho-positions and binding to the dithienothiophene has a high effect of enhancing stability of the radical cation. This is because the steric hindrance groups inhibit the dithienothiophene from being in contact with other molecules.
  • the phenyl groups having substituents at the ortho-positions are present on a plane orthogonal to the plane that is formed by the dithienothiophene skeleton. Accordingly, the bulky phenyl groups having substituents at the ortho-positions function as steric hindrance showing an effect of inhibiting the dithienothiophene skeleton from being in contact with other molecules (cage effect).
  • Fig. 1 shows a steric structure of a molecule when A and A' of the organic compound according to the present invention are phenyl groups.
  • the reference numeral 1 designates a dithienothiophene skeleton, and the reference numeral 2 designates a phenyl group.
  • the dithienothiophene skeleton serving as the core is prevented from coming into intermolecular contacts with other molecules by the phenyl groups as A and A'.
  • each phenyl group portion (cage portion) having the steric hindrance groups A and A' plays a role of protecting the oxidation coloring portion (core portion) from attack by other substrates present as, for example, another electrochromic material molecule or an impurity. Therefore, the cage portion can have a molecular shape of covering the core portion.
  • the substituents introduced into the phenyl groups can be more bulky and can have a ring structure rather than a methyl group.
  • the cage portion and the core portion can have less electronic resonance structures.
  • bleeding of highest occupied molecular orbital (HOMO) locally present in the core portion to the cage portion can be decreased by reducing the electronic resonance effects of the cage portion and the core portion.
  • the molecular orbital cannot be completely interrupted due to quantum-chemical fluctuation.
  • the phenyl group serving as the cage portion connected to the core portion can be orthogonal to the molecular plane of the core portion. In this viewpoint, both ortho-positions, rather than only one ortho-position, of the phenyl group can be substituted with substituents.
  • a cage portion can have an oxidation potential relatively higher than that of the core portion and have a structure to be hardly oxidized. It is conceivable that in such a configuration, the radical cation in oxidation is localized in the core portion to block attack from the outside of the molecule, resulting in a remarkable improvement in stability of the radical cationic state.
  • the substituents A and A' of the phenyl group in the cage portion can be those having electron-donating properties.
  • the substituent having a high electron-donating property and high steric hindrance include an isopropoxy group, a t-butoxy group, and an ethylhexyloxy group.
  • a and A' in General Formula [1] are identical alkyl groups or aryl groups.
  • the structures represented by these A and A' are present at the ortho-positions of the substituted phenyl group and thereby function as a skeleton to protect the dithienothiophene structure of the core by the steric hindrance. Accordingly, an EC device including such a compound as an EC material has high durability against repetition of an oxidation-reduction reaction.
  • one of A and A' in General Formula [1] is a hydrogen atom, and the other is an alkyl group or an aryl group.
  • the alkyl group or the aryl group has a bulky structure or a long alkyl chain, only one of the substituents A and A' can protect the dithienothiophene structure of the core.
  • the phenyl groups may each have an alkyl group having 1 to 4 carbon atoms as a substituent, and n is 1 or 2.
  • the compound according to the present invention can be synthesized using the reaction shown by the Formulae [3] below.
  • X represents a halogen atom.
  • the compound can be synthesized by a coupling reaction, catalyzed by a Pd catalyst, of a combination of a halogenated dithienothiophene and a boronic acid or boronic ester compound of a phenyl group having substituents at the ortho-positions or a combination of a boronic acid or boronic ester compound of dithienothiophene and a halogenated phenyl group having substituents at the ortho-positions.
  • a first aspect of the electrochromic device is a device including a pair of electrodes and an electrochromic layer and an ion conductive layer that are disposed between the pair of electrodes.
  • This electrochromic layer includes the organic compound according to the present invention.
  • the EC device according to the embodiment can be obtained by forming a film of the organic compound according to the present invention on an electrode substrate.
  • the method of forming the film is not particularly limited, but a thin film can be formed by a known method, for example, by dissolving the compound in an appropriate solvent and applying it by a known coating method (e.g., spin coating, dipping, casting, an LB method, or an ink-jetting method), vacuum deposition, ionized vapor deposition, sputtering, or plasma coating.
  • the solvent that is used in the solution for a coating method is not particularly limited as long as it can dissolve the EC compound and can be removed by volatilization after application, and examples thereof include dimethyl sulfoxide, dimethylacetamide, dimethyl formamide, N-methylpyrrolidone, propylene glycol methylether acetate, dimethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, dioxane, methanol, ethanol, propanol, chloroform, toluene, xylene, methyl ethyl ketone, and cyclohexanone.
  • the ion conductive material used in the ion conductive layer is not particularly limited as long as it is an ion-dissociative salt that has good solubility in a solution or high compatibility to a solid electrolyte and contains an anion having an electron-donating property being enough for coloring the EC compound.
  • a liquid ion conductive material, a gelatinized-liquid ion conductive material, or a solid ion conductive material can be used.
  • the liquid ion conductive material can be one in which a supporting electrolyte such as a salt, an acid, or an alkali is dissolved in a solvent.
  • a supporting electrolyte such as a salt, an acid, or an alkali
  • the solvent is not particularly limited as long as it can dissolve the supporting electrolyte, but one having polarity can be particularly used.
  • water and organic polar solvents such as methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, ⁇ -butyrolactone, ⁇ -valerolactone, sulfolane, dimethyl formamide, dimethoxyethane, tetrahydrofuran, propionitrile, dimethylacetamide, methylpyrrolidinone, and dioxolane.
  • organic polar solvents such as methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, ⁇ -butyrolactone, ⁇ -valerolactone, sulfolane, dimethyl formamide, dimethoxyethane, tetrahydrofuran, propionitrile, dimethylacetamide, methylpyrrolidinone, and dioxolane.
  • the salt as the supporting electrolyte is not particularly limited, and inorganic ionic salts such as various alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, and cyclic quaternary ammonium salts can be exemplified.
  • alkali metal salts of Li, Na, and K such as LiClO 4 , LiSCN, LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiPF 6 , LiI, NaI, NaSCN, NaClO 4 , NaBF 4 , NaAsF 6 , KSCN, and KCl; and quaternary ammonium salts and cyclic quaternary ammonium salts such as (CH 3 ) 4 NBF 4 , (C 2 H 5 ) 4 NBF 4 , (n-C 4 H 9 ) 4 NBF 4 , (C 2 H 5 ) 4 NBr, (C 2 H 5 ) 4 NClO 4 , and (n-C 4 H 9 ) 4 NClO 4 .
  • alkali metal salts of Li, Na, and K such as LiClO 4 , LiSCN, LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiPF 6 , LiI, NaI, Na
  • gelatinized-liquid ion conductive material for example, those including the above-mentioned liquid ion conductive material and also a polymer or a gelling agent for increasing the viscosity or for gelation can be used.
  • the polymer (gelling agent) is not particularly limited, and examples thereof include polyacrylonitrile, carboxymethyl cellulose, polyvinyl chloride, polyethylene oxide, polypropylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, polyester, and Nafion (registered trademark).
  • the solid ion conductive material is not particularly limited as long as it is a solid at room temperature and has ion conductivity, and examples thereof include polyethylene oxide, polymers of oxyethylene methacrylate, Nafion (registered trademark), and polystyrene sulfonate.
  • ion conductive materials may be used alone or in a combination of two or more thereof.
  • the electrode material examples include metals and metal oxides such as indium tin oxide (ITO) alloys, tin oxide (NESA), indium zinc oxide (IZO), silver oxide, vanadium oxide, molybdenum oxide, gold, silver, platinum, copper, indium, and chromium; silicon materials such as polycrystalline silicon and amorphous silicon; and carbon materials such as carbon black, graphite, and glassy carbon.
  • ITO indium tin oxide
  • NESA tin oxide
  • IZO indium zinc oxide
  • silver oxide, vanadium oxide, molybdenum oxide gold, silver, platinum, copper, indium, and chromium
  • silicon materials such as polycrystalline silicon and amorphous silicon
  • carbon materials such as carbon black, graphite, and glassy carbon.
  • electrically conductive polymers e.g., polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, and polyethylene dioxythiophene (PEDOT)-polystyrene sulfonate complexes
  • PDOT polyethylene dioxythiophene
  • transparency as an optical filter is also required. Accordingly, those not showing light absorption in the visible light region: ITO, IZO, NESA, and electrically conductive polymers having enhanced electrical conductivity, can be particularly used. These can be used in various forms such as a bulk form or a fine particle form. These electrode materials may be used alone or in a combination of two or more thereof.
  • the method of forming the electrochromic device according to the embodiment is not particularly limited, and the device may be formed by a method in which a film as an EC layer is formed on an electrode substrate, and an ion conductive material is injected into the gap formed between the substrate and a sealed counter electrode substrate by vacuum injection, air injection, or a meniscus method; a method in which an ion conductive material layer is formed on an electrode substrate or on an electrode substrate on which a film as an EC layer is formed, and the substrate is attached to a counter electrode substrate; or a method in which an ion conductive material is used in a film-like form.
  • a second aspect of the electrochromic device is a device including a pair of electrodes and a solution layer serving as the electrochromic layer and the ion conductive layer disposed between the pair of electrodes.
  • the solution layer in this case is not particularly limited as long as the electrochromic material and the supporting electrolyte can be dissolved therein, and those having polarity (high dielectric constant) can be particularly used.
  • water and organic polar solvent such as methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, ⁇ -butyrolactone, ⁇ -valerolactone, sulfolane, dimethyl formamide, dimethoxyethane, tetrahydrofuran, propionitrile, benzonitrile, dimethylacetamide, methylpyrrolidinone, and dioxolane.
  • organic polar solvent such as methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, ⁇ -butyrolactone, ⁇ -valerolactone, sulfolane, dimethyl formamide, dimethoxyethane, tetrahydrofuran, propionitrile, benzonitrile, dimethylacetamide, methylpyrrolidinone, and dioxo
  • the electrochromic device has excellent durability and high transparency when discolored and, thereby, can be suitably used for controlling quantity of incident light to an image pickup element such as a camera or controlling incident wavelength distribution characteristics.
  • the control of incident wavelength distribution is effective for color temperature conversion in image pickup.
  • the light quantity to be received by an image pickup device or incident wavelength distribution characteristics can be controlled by installing the EC device in an optical path of an optical system (lens system) communicating with an image pickup device. Since the EC device in the bleached state can show high transparency, transmitted light in a sufficient quantity relative to the incident light can be obtained. In the colored state, optical characteristics in which incident light is reliably shielded and modulated can be obtained. In addition, excellent oxidation-reduction repeating characteristics and a long operating life can be achieved.
  • Mass-spectrometry (MS) and nuclear magnetic resonance spectrometry (NMR) of compound A-2 gave the results that the molecular weight and the ratio of integrated values of NMR peaks well agreed with the structure of compound A-2. Specifically, 846 as M + of this compound was confirmed by matrix-assisted laser desorption-ionization mass spectrometry (MALDI-MS). The measurement results of nuclear magnetic resonance spectrometry are shown below:
  • the obtained exemplary compound A-2 was dissolved in chloroform, and the absorption spectrum of this solution obtained by measurement with an ultraviolet and visible spectrophotometer (V-560, manufactured by JASCO Corp.) is shown in Fig. 2 .
  • ⁇ max The maximum absorption peak, ⁇ max, was observed at 321.5 nm in the ultraviolet region. Since exemplary compound A-2 did not have absorption over the entire visible light region, it was a transparent material.
  • XX-4 (2,6-dibromodithieno[3,2-b:2',3'-d]thiophene, 200 mg, 0.565 mmol) and 2,4,6-trimethylphenylboronic acid (232 mg, 1.413 mmol) were mixed in a tetrahydrofuran/ethyl alcohol (8 mL/4 mL) mixture solvent, and dissolved oxygen was removed by nitrogen. Then, Pd(PPh 3 ) 4 (32 mg, 0.0285 mmol) and an aqueous solution of 2 M sodium hydroxide (4 mL) were added to the mixture under a nitrogen atmosphere, followed by heating to 80°C and reaction at the temperature for 12 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and subjected to silica gel chromatography (mobile phase: hexane) for isolation and purification to obtain A-17 (28 mg, yield: 12%) as a white solid powder.
  • silica gel chromatography mobile phase: hexan
  • the obtained exemplary compound A-17 was dissolved in chloroform, and the absorption spectrum of this solution was measured with an ultraviolet and visible spectrophotometer as in Example 1.
  • the maximum absorption peak, ⁇ max was observed at 307.7 nm in the ultraviolet region, and no absorption was observed over the entire visible light region.
  • ⁇ max was observed at 307.7 nm in the ultraviolet region, and no absorption was observed over the entire visible light region.
  • XX-4 177.05 mg, 0.50 mmol
  • XX-5 588.6 mg, 1.50 mmol
  • XX-5 is a compound synthesized in accordance with the procedure described in WO2005/054212 .
  • Pd(PPh 3 ) 4 57.8 mg, 0.05 mmol
  • an aqueous solution of 2 M cesium carbonate 1.0 mL
  • Mass-spectrometry (MS) and nuclear magnetic resonance spectrometry (NMR) of compound XX-6 gave the results that the molecular weight and the ratio of integrated values of NMR peaks well agreed with the structure of compound XX-6. Specifically, 724 as M + of this compound was confirmed by matrix-assisted laser desorption-ionization mass spectrometry (MALDI-MS). The measurement results of nuclear magnetic resonance spectrometry are shown below.
  • the obtained compound XX-6 was dissolved in chloroform, and the absorption spectrum of this solution was measured with an ultraviolet and visible spectrophotometer as in Example 1.
  • the maximum absorption peak, ⁇ max was observed at 358.5 nm in the ultraviolet region, and no absorption was observed over the entire visible light region.
  • ⁇ max the maximum absorption peak
  • Compound A-17 obtained in Example 2 compound XX-6 obtained in Example 4, compound XX-8 obtained in Example 6, compound A-1 obtained in Example 7, and, as a comparative compound, compound XX-7 that is DTT having a t-butyl group as a substituent introduced thereinto, the steric hindrance of t-butyl group being smaller than that of the substituent of the present invention, were measured for durability against oxidation-reduction cycles.
  • Compound XX-7 as the comparative compound was synthesized by a Friedel-Crafts reaction of t-butyl bromide (2-bromo-2-methylpropane) and DTT. The structural formula is shown below:
  • the measurement of durability was performed using a working electrode of glassy carbon, a counter electrode of platinum, and a reference electrode of silver and dissolving each compound at a concentration of 1.0 ⁇ 10 -4 mol/L in a dichloromethane solution of tetrabutylammonium perchlorate (0.1 mol/L) serving as a supporting electrolyte.
  • This solution was subjected to a repetitive square-wave potential program that is composed of oxidation at a constant potential of +1.1 V (vs. Ag/Ag+), which is not lower than the oxidation potential of the compound, for 3 seconds and reduction at a constant potential of 0 V (vs. Ag/Ag+) for 3 seconds for 20000 times.
  • Mass-spectrometry (MS) and nuclear magnetic resonance spectrometry (NMR) of compound XX-8 gave the results that the molecular weight and the ratio of integrated values of NMR peaks well agreed with the structure of compound XX-8. Specifically, 524 as M + of this compound was confirmed by matrix-assisted laser desorption-ionization mass spectrometry (MALDI-MS). The measurement results of nuclear magnetic resonance spectrometry are shown below:
  • the obtained compound XX-8 was dissolved in chloroform, and the absorption spectrum of this solution was measured with an ultraviolet and visible spectrophotometer as in Example 1.
  • the maximum absorption peak, ⁇ max was observed at 364.5 nm in the ultraviolet region, and no absorption was observed over the entire visible light region.
  • ⁇ max maximum absorption peak
  • Example 2 In a 50-mL reaction container, XX-2 (526.2 mg, 1.17 mmol) synthesized in Example 1 and XX-3 (1071.2 mg, 3.0 mmol) were reacted as in Example 1 in a toluene/ethyl alcohol/tetrahydrofuran (6 mL/3 mL/8 mL) mixture solvent.
  • Mass-spectrometry (MS) and nuclear magnetic resonance spectrometry (NMR) of compound A-1 gave the results that the molecular weight and the ratio of integrated values of NMR peaks well agreed with the structure of compound A-1. Specifically, 652 as M + of this compound was confirmed by matrix-assisted laser desorption-ionization mass spectrometry (MALDI-MS). The measurement results of nuclear magnetic resonance spectrometry are shown below: 1 H-NMR (THF-d 8 ) ⁇ (ppm): 7.60 (t, 2H), 7.50 (d, 4H), 7.31-7.25 (m, 20H), 6.71 (s, 2H).
  • the obtained exemplary compound A-1 was dissolved in chloroform, and the absorption spectrum of this solution was measured with an ultraviolet and visible spectrophotometer as in Example 1.
  • the maximum absorption peak, ⁇ max was observed at 355 nm in the ultraviolet region, and no absorption was observed over the entire visible light region.
  • ⁇ max maximum absorption peak
  • the absorption peak of oxidized exemplary compound A-1 was at 480 nm in the visible region.
  • Mass-spectrometry (MS) and nuclear magnetic resonance spectrometry (NMR) of compound XX-9 gave the results that the molecular weight and the ratio of integrated values of NMR peaks well agreed with the structure of compound XX-9. Specifically, 468 as M + of this compound was confirmed by matrix-assisted laser desorption-ionization mass spectrometry (MALDI-MS). The measurement results of nuclear magnetic resonance spectrometry are shown below:
  • the obtained compound XX-9 was dissolved in chloroform, and the absorption spectrum of this solution was measured with an ultraviolet and visible spectrophotometer as in Example 1.
  • the maximum absorption peak, ⁇ max was observed at 390 nm in the ultraviolet region, and no absorption was observed over the entire visible light region.
  • ⁇ max maximum absorption peak
  • the organic compounds according to the present invention are neutral and transparent and are materials having high durability against oxidation-reduction repetition.
  • the EC devices are highly transparent not to show optical absorption in the visible light region when bleached and are excellent in durability and are stable.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
EP11800650.1A 2010-06-30 2011-06-10 Organic compound and electrochromic device including the same Not-in-force EP2588484B1 (en)

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JP5932787B2 (ja) 2011-06-07 2016-06-08 キヤノン株式会社 エレクトロクロミック素子
WO2013023109A1 (en) * 2011-08-10 2013-02-14 Georgia Tech Research Corporation Coupled heteroaryl compounds via rearrangement of halogenated heteroaromatics followed by oxidative coupling (coupled tricyclic core compounds)
WO2013023106A1 (en) * 2011-08-10 2013-02-14 Georgia Tech Research Corporation Coupled heteroaryl compounds via rearrangement of halogenated heteroaromatics followed by oxidative coupling (acyl moieties)
WO2013023108A1 (en) * 2011-08-10 2013-02-14 Georgia Tech Research Corporation Coupled heteroaryl compounds via rearrangement of halogenated heteroaromatics followed by oxidative coupling (heteroarylene spacer moiety)
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US20130100517A1 (en) 2013-04-25
JP5721491B2 (ja) 2015-05-20
US8982443B2 (en) 2015-03-17
EP2588484A4 (en) 2013-12-04
JP2012180333A (ja) 2012-09-20
WO2012002185A1 (en) 2012-01-05

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